CN101945690A - Be used for the partition method of the multicolumn of isolating ions metal derivative by sequence - Google Patents

Be used for the partition method of the multicolumn of isolating ions metal derivative by sequence Download PDF

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CN101945690A
CN101945690A CN2008801271499A CN200880127149A CN101945690A CN 101945690 A CN101945690 A CN 101945690A CN 2008801271499 A CN2008801271499 A CN 2008801271499A CN 200880127149 A CN200880127149 A CN 200880127149A CN 101945690 A CN101945690 A CN 101945690A
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district
displacement
post
outlet
inlet
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CN101945690B (en
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M-A·斯奥雷尔
F·古拉
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Novasep Process SAS
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Applexion SAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1821—Simulated moving beds
    • B01D15/1828—Simulated moving beds characterized by process features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1821—Simulated moving beds
    • B01D15/185—Simulated moving beds characterized by the components to be separated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/42—Selective adsorption, e.g. chromatography characterised by the development mode, e.g. by displacement or by elution
    • B01D15/422—Displacement mode
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention relates to the partition method and the device that be used to implement described method of multicolumn by sequence.The present invention is specially adapted to separate the metal derivative that exists in the lixiviate effluent in the hydrometallurgical processes, for example uranium, nickel, copper, cobalt and other noble metal.

Description

Be used for the partition method of the multicolumn of isolating ions metal derivative by sequence
Technical field
The present invention relates to the partition method and the device that be used to implement described method of multicolumn by sequence.The present invention is specially adapted to separate the metal derivative that exists in the lixiviate effluent in the hydrometallurgical processes, for example uranium, nickel, copper, cobalt and other noble metal.
Background technology
The normal few techniques of using is extracted the metal object class in metal industry.Especially, have under the situation of low metal derivative content, use microwave leaching technology, comprise by extracting the soluble metal part with suitable solubilizer lixiviate at the ore of extraction.In case this metal derivative dissolves with ionic species, then subsequent step comprises required thing class and impurity or other separated from contaminants.
This partition method is characterised in that, makes one or more liquid phases (being known as " phase flows ") and solid phase (being known as " fixing mutually ") contact.As the situation in the ion-exchange chromatography, inject the ionic metal derivative and fixing one or more interactions of setting up various character mutually of liquid phase.Therefore its displacement in chromatogram arrangement is different from the displacement of other products contained in the charging of being processed.Based on interactional this species diversity, can purify or make this ionic metal derivative to be enriched in one of fraction.
Proposed to carry out the method for continuous ionic exchange.US-A-2815332 has described a kind of closed-circuit system, and wherein resin is advanced with the flow direction opposite with liquid.Four districts that separated by valve and be respectively applied for saturated, rinsing, regeneration and rinsing are contained in this loop.Resin advances to next compartment with the flow direction opposite with liquid phase from a compartment under the waterpower pulse effect in these districts.
Some author has developed the system that is used for the chromatographic SMB of being known as (simulation moving-bed).For example, US-A-2985589 has described continuous chromatography SMB, wherein chromatography resin is fixed, and be distributed in several compartments, but the periodicity of the position by fluid intake and outlet moves moving of simulation resin.Entry position (charging and eluant, eluent) and exit position (extract and extract remainder) delimited four districts then.US-A-6375851 has described the system with six districts, the transformation of the ion-exchange of the method that this describes in US-A-2985589 before being.Except that regeneration step (carrying out under its situation about moving ahead of the curve), the system of describing among the US-A-6375851 is based on SMB.Fluid intake and outlet therefore usually side by side, after a sequence same moved further.
In all these systems, the author provides the circulation fully continuously of all fluids.These systems cause very large post quantity, and column dimension is determined by the minmal sequence of this sequence.
For method used in the hydrometallurgy,, systematically after production and regeneration step, carry out rinse step particularly as the ion-exchange among the WO 2007/087698.In batch process, these steps are the most normal carries out with iptimum speed with respect to fixing or desorption kinetic.Therefore, prior art can not be implemented economic favourable extensive partition method, because its resin that need be used for post and be used for the mistake a large amount of elaboration products.None can be implemented the whole process-cycle continuously to consider at present used method, and particularly in the regeneration of resin step, this shortcoming is more practical.
Except this shortcoming, all these methods all relate to the regenerative agent of very a large amount of water of in being usually located at the minery of desert area use and quite a large amount of highly acidic as a rule.Except that economic problems, also face the protection of ecological problem and environmental resource.
Brief summary of the invention
The present invention relates to a kind of commercial scale method, this method has been optimized the amount of the regenerative agent, resin and the water that relate in the separation cycle of the ionic metal derivative that exists in the extracting solution, and therefore can provide better working ability for the mine development facility.Method of the present invention protection environment can obtain the high yield of required metal derivative, and has more advantages than the method for prior art economically.
This is undertaken by the partition method on resin especially---and make the extracting solution that contains the ionic metal derivative comprise at least three districts, pass through on the fixed bed of the selective resin of the material of being considered, thereby becoming the selectivity of sequence to retain by multicolumn makes the ionic metal derivative separate with described extracting solution, between the adjacent region and in the end between a district and first district liquid flow device is being set, this method comprises several sequences, each sequence comprise at least one can be simultaneously or do not carry out simultaneously be selected from adsorption step, rinse step, the step of desorption procedure, the sequence of each back is following carries out: made the forward position in these districts move essentially identical increment downstream before the periodicity of introducing point and off-take point moves.
This method can comprise the subsequence under the situation of not injecting charging.
According to a further aspect in the invention, the method is characterized in that it comprises several sequences, each sequence comprises at least one following step:
(a) introduce the rinsing solution of certain volume and substantially side by side take out the diluted liquid of described ionic metal derivative of equal volume in the porch in first district in the position that is positioned at downstream, described district;
(b) introduce the described charging extracting solution of certain volume in the porch in second district, with the liquid that is rich in the relative impurity of more not retaining that substantially side by side takes out equal volume in the position that is positioned at downstream, described district;
(c) introduce the rinsing solution of certain volume and substantially side by side take out the diluted liquid of regenerative agent of equal volume in the porch in the 3rd district in the position that is positioned at downstream, described district;
(d) randomly introduce the decontamination agent of certain volume and substantially side by side take out the dilution of equal volume in the position that is positioned at downstream, described district in the porch in the 4th district,
(e) introduce the eluant, eluent of certain volume and substantially side by side take out the liquid that is rich in described metal derivative of equal volume in the porch in the 5th district in the position that is positioned at downstream, described district;
Step (a) and (b), (c), (d) and (e) can carry out simultaneously or not carry out simultaneously;
The sequence of each back be by introduce point and off-take point periodically downstream the increment of mobile basic identical volume carry out;
Also comprise step:
(f) before the periodicity displacement, at least zone (b) and (e) in the displacement in forward position.
According to another embodiment of the present invention, the method is characterized in that it comprises several sequences, each sequence comprises following step:
(a) elder generation that introduces the equilibrium liquid of certain volume in the porch in first district and substantially side by side take out equal volume in the position that is positioned at downstream, described district is made of the liquid that is made of balance solution then actified solution;
(b) introduce the charging extracting solution to be processed that contains the ionic metal derivative of certain volume in the porch in second district, with the liquid that contains the relative impurity of more not retaining that substantially side by side takes out equal volume in the position that is positioned at downstream, described district;
(c) introduce the rinsing solution of certain volume and substantially side by side take out the diluted liquid of impurity of the less retention of the described ionic metal derivative of ratio of equal volume in the porch in the 3rd district in the position that is positioned at downstream, described district;
(d) introduce the elute soln of certain volume and substantially side by side take out the liquid that contains described ionic metal derivative of equal volume in the porch in the 4th district in the position that is positioned at downstream, described district;
(e) introduce the actified solution of certain volume and substantially side by side take out the liquid of the impurity that contains the easiest retention of equal volume in the porch in the 5th district in the position that is positioned at downstream, described district,
Step (a) and (b), (c), (d) and (e) can simultaneously or not carry out simultaneously;
The sequence of each back be by introduce point and off-take point periodically downstream the increment of mobile basic identical volume carry out,
Also comprise step
(f) before the periodicity displacement, the displacement in the forward position in the zone (c) at least.
According to another embodiment of the present invention, the method is characterized in that step (d) and (e) carry out, these steps thereby be equivalent to the step of following formation with same fluid:
(d) introduce the regenerative agent of certain volume and substantially side by side take out the liquid that is rich in described ionic metal derivative of equal volume in the porch in the 4th district in the position that is positioned at downstream, described district;
The the 4th and the 5th district thereby be merged into the 4th single district.
According to another embodiment of the present invention, the method is characterized in that step (a) and (b), (c) and (d) carry out simultaneously to small part.
According to another embodiment, the method is characterized in that the described displacement in forward position makes the forward position synchronous shift in the same district not.
According to another embodiment, the method is characterized in that the displacement in forward position comprises the steps:
(i) do not setting up the closed circuit district between the same district from five districts, first district to the; With
(ii) in described loop, circulate so that the forward position displacement.
According to another embodiment of the present invention, the displacement in forward position comprises the steps:
(i) be connected with the fluid of second district inlet by the outlet of first district and be connected by the fluid of second district outlet with the 3rd district inlet, set up first displacement field, and the displacement downstream of the inlet in first district with the outlet displacement upstream in inlet that first displacement field is provided and the 3rd district so that the outlet of first displacement field to be provided; With
Is connected with the fluid of the 4th district inlet and exports the fluid that enters the mouth with the 5th district by the 4th district and be connected and export the fluid that enters the mouth with first district with the 5th district and be connected by the 3rd district outlet, set up second displacement field, and the displacement downstream of the inlet in the 3rd district with the outlet displacement upstream in the inlet that second displacement field is provided and first district so that the outlet of second displacement field to be provided; With
(ii) introduce the rinsing solution of certain volume and substantially side by side take out the rinsing solution of the recovery of equal volume in the exit of first displacement field in the porch of first displacement field;
(iii) introduce the rinsing solution of certain volume and substantially side by side take out the rinsing solution of the recovery of equal volume in the exit of second displacement field in the porch of second displacement field.
According to another embodiment of the present invention, the described displacement that the method is characterized in that the forward position makes the forward position synchronous shift in the same district not.
According to another embodiment of the present invention, the method is characterized in that the displacement in forward position comprises the steps:
(i) be connected with the fluid of second district inlet by the outlet of first district and be connected, set up first district of first displacement by the fluid of second district outlet with the 3rd district inlet; With
Is connected with the fluid of the 4th district inlet and exports the fluid that enters the mouth with the 5th district by the 4th district and be connected and export the fluid that enters the mouth with first district with the 5th district and be connected by the 3rd district outlet, set up second district of first displacement; With
(ii) introduce the described solution of certain volume and substantially side by side at the regenerative agent liquid of the dilution of the equal volume of the exit taking-up equal volume in first district of first displacement in the porch of first displacement field;
(iii) introduce the regenerative agent of certain volume and substantially side by side at the diluted liquid of described ionic metal derivative of the exit taking-up equal volume in second district of first displacement in the porch of second displacement field;
(iv) be connected with the fluid of second district inlet and be connected by the fluid of second district outlet with the 3rd district inlet by the outlet of first district, set up first district of second displacement, and the displacement downstream of the inlet in first district is with the outlet displacement upstream in the inlet in first district that second displacement is provided and the 3rd district outlet with first district that second displacement is provided; With
(v) be connected with the fluid of the 4th district inlet with being connected with the fluid of the 5th district outlet with the fluid of the 5th district inlet and be connected with first district inlet by the outlet of the 4th district by the outlet of the 3rd district, set up second district of second displacement, and the displacement downstream of the inlet in the 3rd district with the outlet displacement upstream in the inlet that second displacement field is provided and first district so that the outlet of second displacement field to be provided; With
(vi) introduce the rinsing solution of certain volume, with substantially side by side at the liquid that is rich in the relative impurity of more not retaining of the exit taking-up equal volume in first district of second displacement in the porch in first district of second displacement;
(vii) introduce the rinsing solution of certain volume and substantially side by side at the liquid that is rich in described ionic metal derivative of the exit taking-up equal volume in second district of second displacement in the porch in second district of second displacement.
According to another embodiment of the present invention, the method is characterized in that step (f) is included in the displacement in the forward position in all districts before the periodically displacement.
According to another embodiment of the present invention, the method is characterized in that the periodicity displacement of injection point is carried out from a post to a post ground.
According to another embodiment of the present invention, the method is characterized in that the periodicity displacement of injection point is carried out from two posts to two post ground.
According to another embodiment of the present invention, the method is characterized in that described district comprises at least one post, preferably at least two posts.
According to another embodiment of the present invention, the method is characterized in that the dilatation of described introducing point and described off-take point displacement is equivalent to the volume of the entire portion in absorbing material district substantially.
According to another embodiment of the present invention, the method is characterized in that the dilatation of described introducing point and described off-take point displacement is equivalent to column volume substantially.
According to another embodiment of the present invention, post is furnished with banked direction control valves.
According to another embodiment of the present invention, the method is characterized in that the periodicity displacement of described step is synchronous.
According to another embodiment of the present invention, the method is characterized in that the periodicity displacement of these steps is nonsynchronous.
According to another embodiment of the present invention, the method is characterized in that described liquid to the small part that described metal ion derivative is diluted is sent to step (b).
According to another embodiment of the present invention, the method is characterized in that and have additional zone, and be characterised in that it also comprises step (g) is introduced all or part of diluted liquid of described metal ion derivative that obtains described additional zone and reclaimed basic identical volume in the position that is positioned at downstream, described district in step (a) rinsing solution.
According to another embodiment of the present invention, the method is characterized in that step (b) comprises two sub-steps (b1) and (b2) and the intermediate steps that is used to regulate the parameter (particularly regulating by changing change pH values) of this solution.
According to another embodiment of the present invention, the method is characterized in that diluted described liquid to the small part of regenerative agent that will obtain in the step (c) is sent to step (d), may be after finishing.
According to another embodiment of the present invention, the method is characterized in that and send rinsing solution to the small part of described recovery back to step (a) and/or (c).
According to another embodiment of the present invention, method of the present invention comprises at least 3 posts and 4 fluid lines.
According to another embodiment of the present invention, the method is characterized in that described chromatography is the ion-exchange type, and described ionic metal derivative is the salt that is selected from the complex compound of uranium, gold, copper, zinc, nickel, cobalt and PGM, preferably the salt of uranium, particularly uranous sulfate.
According to a preferred embodiment, this regeneration step comprises the pollution control step with the highly basic of for example potassium hydroxide or NaOH type, randomly uses afterwards the step of water rinse, then the step of regulating this resin again with acid, for example sulfuric acid.
According to another embodiment of the present invention, the method is characterized in that this eluant, eluent is a sulfuric acid.
At last, the present invention relates to be used to implement the pollution control device of method of the present invention.
The accompanying drawing summary
-Fig. 1 is the diagram according to the SMB embodiment of prior art situation;
-Fig. 2 is in the diagram of facility center pillar in its environment according to one embodiment of the invention;
-Fig. 3 is the diagram of first embodiment;
-Fig. 4 is the diagram of second embodiment;
-Fig. 5 is the diagram of the 3rd embodiment;
-Fig. 6 is the diagram of the 4th embodiment;
-Fig. 7 is the diagram according to the SMB embodiment of prior art situation;
-Fig. 8 is the diagram that is equivalent to the forward position displacement of transitional sequence according to one embodiment of the invention;
-Fig. 9 is the diagram according to the asynchronous displacement of the rinsing solution infusion line of another embodiment of the present invention;
-Figure 10 is the diagram according to the asynchronous displacement of the charging circuit of another embodiment of the present invention and transitional sequence;
-Figure 11 has shown the inventive method with 6 fluid lines;
-Figure 12 has shown the different sequences of using the inventive method that 5 kinds of fluids carry out;
-Figure 13 has shown method of the present invention.
In these figure, use following symbol:
W water
The ionic metal derivative that FD is diluted
F contains the extracting solution (containing charging solution or " charging " of required metal object class) of ionic metal derivative
The RAF extract remainder
The actified solution of RD dilution
The R regenerative agent
The EXT extract
The displacement of displ material
Ads absorption
Pre ads adsorbs in advance
Water displ. water level moves (rinsing)
Water water
H 2SO 4Displ. water level moves (regeneration)
Spare is standby
The Wash washing
Rege regeneration
Wash neutral washs neutral
Acidified Water acidifying water
The Waste waste liquid
The Step time step time
The Step step
Detailed Description Of The Invention
According to the present invention, the ionic metal derivative refers to the ionized metal complex compound of any type, particularly and be not limited to, the complex compound that is formed by uranium and gold and in the extraction process of copper, zinc, nickel, cobalt and PMG (platinum group metal), obtain those. The complex compound that this metal derivative is preferably formed by uranium is more preferably uranous sulfate. Counter ion counterionsl gegenions can be sulfate radical, carbonate or other. In sulfuric acid solution, uranium (IV) is mainly with UO especially2+ 2The uranyl cationic form, and with sulfate composite salt form UO2SO 4、UOS(SO 4) 2- 2Deng existence. In the following description, represent the ionic metal derivative as an example of uranium example, but scope of the present invention not only is limited to this product.
According to the present invention, extracting solution refers to that it contains the metal derivative of the as defined above ionic species of dissolved form or suspended form by any solution of hydrometallurgical extraction method generation. This lixiviate composition is depending on the geologic property of the ore of exploitation in nature. Therefore, for example, that the extracting solution of uranium ore contains is about 100 to 500, the about uranium of 350ppm for example, about 200 to 1000, the about silica of the amount of 500ppm for example, about 500 to 20,000, the about iron of the amount of 1000ppm for example are as the thing class of main existence, and other compound, for example vanadium. The extracting solution of copper mine contains 1 to 5 grams per liter, the copper of about 3 grams per liters for example, 3 to 10 grams per liters, the iron of about 6 grams per liters for example, and 100 to 1000ppm, the about silica of 400ppm for example, and other impurity, for example aluminium or manganese.
In fact, the iron in the vanadium in the uranium situation or the copper situation, modal pollutant comprises from those of gangue, particularly silicate. These impurity can disturb the abstraction technique of required thing class, tend to be attached on the resin, limit thus their exchange capacity.
According to the present invention, the ionic metal derivative can be fixed and retain mutually most, also can least be fixed and retain mutually. For example, when absorption method of the present invention during for separating of the thing class of uranium and so on, impurity is fixed and retains mutually and the ionic metal derivative is least retained most.
According to the present invention, adsorption step refers to following step: inject the charging that contains the ionic metal derivative to be separated in this process, one or more contained in this charging products are attached on the solid phase then. This step is equivalent to the loading of this phase.
According to the present invention, desorption procedure refers to following step: in this process, the product that is attached on the solid carrier enters liquid phase. Therefore adsorption process comprises at least one adsorption step and at least one desorption procedure naturally.
According to the present invention, rinse step refers to upgrade thus liquid phase contained in the post in sorption and desorption step or the step between desorb and adsorption step. This step also can be known as washing step.
Method of the present invention can be optimized the charging sequence of the extracting solution that will process and the rinsing of isolated product better; Thereby reduce used volume and still less produce accessory substance.
In addition, method of the present invention provides one or several following advantage:
-because post is fixed, this Machine Design can be avoided moving-member. Post is small-sized and can uses banked direction control valves at each post.
-the maintenance simplified just can make a post separate with this circulation because needn't stop the method, with replacing resin or chromosorb, generally safeguard etc. This maintenance requirement is closer to the requirement of known relatively low batch process.
-technology controlling and process is simple, just can change the method and regulate the zone (not needing to change mechanical part) of the method because only need to change the parameter of machine. For each processing step, also can be on each post the use traffic meter.
-increase post and revise technological parameter to revise these zones by simple on existing post, implement easily capacity extensions.
If be suitable for, in following description, explain these and other advantage.
For Fig. 1,3 to 6, provide a description with reference to the salt (sulfate) of uranium, but it being understood that the inventive method applicable to all ionic metal derivatives, and be applicable to the chromatography that well known to a person skilled in the art any type.
As prompting, will reaffirm that in the situation of ion-exchange, the ionic metal derivative is regarded as extract (X), because it is more exchanged, difficult exchanged impurity is regarded as extract remainder (R). In other example of the application, use identical agreement, when not having ion-exchange, use term " easier retention " or " more not retaining ".
Ion exchange resin is conventional, and rinsing and actified solution also are. In said case with for the metallic compound of ionic species, use I type or II type reinforcing yin essence ionic resin (with the polystyrene-divinylbenzene polymer of quaternary amines, Amberjet 4400 Cl for exampleTM、Amberlite920U Cl TM、Dowex 21 K TM) or weak anionic type resin. In the situation of metallic compound that is cationic form, use strong cation type resin (with the polystyrene-divinylbenzene polymer of sulfo group, for example Amberlite IR252TM) or weak cation type resin. In some cases, use selective resin (with the polystyrene-divinylbenzene polymer of specific chelation group). These different resins are gels or have suitable distribution of particles (uniformity coefficient is near 1.1; 0.3 to 1.6 millimeter of effective size of grain) the big molecule type of curing.
From this angle, the present invention does not protrude from the prior art situation of ion-exchange. Can use according to circumstances weak or strong anionic or cation type resin.
Also can use several systems of series connection; Especially, can use cation type resin the first system, carry out demineraliting succeeded by the second system that contains the anionic resin.
The following description of three embodiments that the Fig. 3 to 5 by the reference accompanying drawing makes illustrates the present invention, and Fig. 1 has described the embodiment according to prior art.Use the representative example of uranium salt, the material that representative will be purified in ion-exchange chromatography as the ionic metal derivative.
With reference to Fig. 1, this facility comprises 8 posts 1,2,3,4,5,6,7 and 8 that covered by ion exchange resin.Explained later is according to the operation of this SMB type facility of prior art.Shift step is carried out from left to right, and in fact this be equivalent to post and move from right to left.
Step (a) comprises and is intended to the operation introducing the water W of certain volume and substantially side by side take out the dilution slaine of equal volume in the exit of post 2 in the porch of post 1, post 1 and 2 formation, first district.In introducing the process of water, just when the beginning in this stage, because displacement, therefore post 1 is actually just (before this displacement) post 2 before.Just Zhi Qian post 2 is filled with the uranium salt solution (not by the fixing uranium salt solution of ion-exchange) of dilution.Therefore the pure water forward position moves down, and therefore post 1 becomes " water " state (having the uranium salt that is exchanged in this post) from " uranium salt of dilution " state (it being understood that the uranium salt that existence is exchanged this post).Post 2 is the posts 3 before just, become " uranium salt of dilution " state (having the uranium that fixing quilt exchanges) from " uranium salt " state (having the uranium that fixing quilt exchanges), reclaim the ionic metal derivative extracting solution that to purify of dilution attitude in post 2 bottoms, denseer relatively, more and more rarer then at first.In fact, on this post, no longer include available exchange site, so this dilute solution is just simply along this post wash-out; This is the displacement of uranium solution.The dilute solution of this recovery is sent the original storage tank of the solution that will purify usually back to, directly delivers to post 3 tops after probable.
Step (b) comprises and is intended to introduce in the porch of post 3 the described extracting solution of certain volume and substantially side by side in the operation of the liquid that is rich in extract remainder of the exit of post 4 taking-up equal volume.To post 3 supply extracting solutions, but the post 4 of this post before being equivalent to just, therefore be that part has exchanged uranium salt and also contained as yet the not post of the dilution uranium salt of exchange.Similarly, therefore the post 5 before post 4 is equivalent to just is moisture post.Post 4 is pre-adsorption columns, because it receives the uranium salt solution that post 3 is discharged.In post 3, inject uranium salt solution, and saturated forward position advances in post 3, and the forward position of extracting solution and in the propelling in post 4 (pre-adsorption column) of the exchange on these sites, exit at post 4, reclaim extract remainder, promptly the solution that will process not with the composition of resins exchange, become solution with higher extract remainder concentration from very rare solution.
The water of certain volume is introduced and substantially side by side in the operation of the diluted liquid of the regenerative agent of the exit of post 6 taking-up equal volume in the porch that step (c) is included in post 5.To post 5 supply water, post 6 is discharged the regenerative agent of dilution simultaneously.Therefore in fact, post 6 is posts 7 before displacement just, and just after displacement, the effluent that it receives post 5 promptly contains the water of a little regenerative agent.Therefore the effluent of post 6 is the regenerative agent of dilution.
The regenerative agent of certain volume is introduced and substantially side by side in the operation of the liquid that is rich in slaine of the exit of post 8 taking-up equal volume in the porch that step (d) is included in post 7.To post 7 supply regenerative agents, and post 7 links to each other with post 8.This post 8 is posts before displacement 1 just, therefore just after displacement, to post 8 supply regenerative agents, this advances the regenerative agent forward position in post 8, reclaim extract then in post 8 bottoms, is rare at first, more and more denseer then, and when yield begins to reduce, make the step displacement.
Therefore, when given sequence N finishes, have water at the top of post 1 and be fixed on the uranium salt that the quilt on the resin exchanges.At the top of post 2, there are the uranium salt, water and the residual uranium salt solution that will purify that are exchanged.At the top of post 3, there are the uranium salt of exchange fully and the extracting solution that will purify.At the top of post 4, there be uranium salt (site does not have to be exchanged fully) and the extract remainder (the not attachment portion of the extracting solution that will purify) and the residual extracting solution that will purify of part exchange.At the top of post 5, there are washings and prepare the resin sites of exchange.At the top of post 6, there are the diluted washings of regenerative agent, the site is reproduced.At the top of post 7, there be the site (preparing the exchange uranium salt) and the actified solution of holomorphosis.At the top of post 8, there are the site of partial regeneration and the actified solution and the extract (part) of dilution.
Therefore, when next sequence N+1 has just begun, make post to the figure that moves to left, have following position thereupon with reference to moving right by injection and off-take point.Water is delivered on the post 2, and this post has uranium salt, water and the residual extracting solution that will purify that is exchanged at its top.At the top of post 3, there are the uranium salt of exchange fully and the extracting solution that will purify, it receives the effluent of post 2 then.At the top of post 4, there be uranium salt (site does not have to be exchanged fully) and the extract remainder (the not attachment portion of the extracting solution that will purify) and the residual extracting solution that will purify of part exchange, this post receives the extracting solution that will purify then.At the top of post 5, there are washings and prepare the resin sites of exchange, it receives the effluent of post 4, i.e. extract remainder and useless uranium salt solution, it will exchange on this pre-adsorption column.At the top of post 6, on post, supply washings with regeneration site and the regenerant solution that contains dilution.The post 7 that also has the site (preparing the exchange uranium salt) of holomorphosis receives then from the water of post 6 and the actified solution of its dilution of removing in the bottom.At the top of post 8, there are the site of partial regeneration and the actified solution of dilution, and to tower 8 supply regenerant solution.
Therefore, it is as follows to enter the stream of column top.At the top of post 2, extracting solution is come at the top to have on the post of uranium salt of part exchange.So gradient that the cracking in forward position takes place and do not deferred to.At the top of post 8, actified solution is come on the post of regenerative agent partial regeneration with dilution, therefore carries out with the mixture of pure regenerative agent and impure regenerative agent partly.Still do not defer to gradient.
Therefore finding out to have the advantage that is continuous although be used for the typical SMB system in ion exchange resin field, but still be not immaculate, is responsive aspect regeneration especially.
Because the step of the forward position displacement in the zone before the periodicity displacement, the present invention can remove this problem and defer to gradient.Usually a post is implemented forward position displacement step.Following description relates to three kinds of embodiments.Selected fluid by injecting post or by closed loop cycle inject existing fluid, by injecting water (rinsing liquid) or injecting water then, enforcement forward position displacement by injecting charging and regenerative agent.
In Fig. 3,4 and 5, facility is identical aspect post, has only the operational mode difference of post and may have middle bucket (not shown).
This facility comprises and is applicable to the present invention and the post (1,2,3,4,5,6,7 and 8) that covers of one of resin as defined above by same amount.
These post arranged in series include an inlet and an outlet separately.Generally speaking, as follows, each inlet can receive water, the uranium salt of acidifying, the sulfuric acid of the pending aqueous solution, actified solution, water, recovery.Usually, as follows, each outlet can produce uranium salt, extract remainder, extract, the water of recovery, the sulfuric acid of dilution, the uranium salt (extract) of dilution.Each post also links to each other with the upstream and downstream post.
This principle is presented among Fig. 2.As shown in Figure 2, valve can be a banked direction control valves, has 6 tunnel valve especially.These banked direction control valves itself are known, use Motor Control traditionally.Advantageously, under operational mode, start valve with each rotation one increment.For some pattern, valve can be started so that they rotate several sectors, for example when wish separating a post when on this post, marching to particular sequence.
With reference to first embodiment shown in Fig. 3, mark is done after the sequence N of sequence 1.1 in the figure, has the layout of describing above with reference to the SMB system.
Mobile forward position in the process of sequence 1.2 then.This displacement obtains by post being placed the loop and entering circulation.
By fluid is circulated in this loop, make displacement carry out an increment of a post.The volume of displacement is equivalent to the volume of post.
Therefore when sequence N+1 begins, obtain following post.Therefore post 4 has the site of part exchange at the top, and with regard to fluid, has the material (site that has exchanged is constant) at post 3 tops, therefore is extracting solution (therefore being the basic identical composition that next will receive with this post) to be purified.Post 8 has the site and regenerant solution (therefore being the basic identical composition that next will receive with this post) of partial regeneration then.Therefore, carry out the supply of post, because at the top of these posts, concentration is constant with constant gradient.The situation of other post also is like this.Post 6 has the material at post 5 tops at the top, i.e. water, and also receive water.Post 2 has the material of post 1 at the top, i.e. water, and also receive water.
With reference to second embodiment shown in Fig. 3, mark is done after the sequence N of sequence 1.1 in the figure, has the layout of describing above with reference to the SMB system.
Mobile forward position in the process of sequence 1.2 then.This displacement obtains by making two displacement fields enter circulation.First displacement field is the district that comprises post 2,3,4 and 5.Second displacement field is the district that comprises post 6,7,8 and 1.
Inject water by top, make displacement carry out an increment of a post at displacement field.The volume of displacement is equivalent to the volume of a post.
Therefore when beginning, sequence N+1 obtains as the post in first embodiment.Difference is from the displacement of water column volume.In fact, between these two parts of production/regenerative process, exist the water buffering to avoid the not pollution of jljl class.This water buffering simply shifts out in the first embodiment, and replaced in second embodiment.In second embodiment, therefore the water volume in the bottom of post 1 and 5 recovery post is the water (Rec W) that reclaims then.The water of this recovery is sent to middle pond, and can be used for to post supply washings.Also can partly use this water to carry out rinsing with fresh water.In other sequence and first embodiment those are similar.
In first and second embodiments, the displacement in forward position is synchronous, because a dilatation is moved in all forward positions simultaneously.Forward position that enters and the same moved further in the forward position of leaving.
In first and second embodiments, do not have subsequence that charging injects and be equivalent to subsequence 1.2 (or 2.2, depend on the sequence of being considered).
With reference to the 3rd embodiment shown in Fig. 5, mark is done after the sequence N of sequence 1.1 in the figure, has the layout of describing above with reference to the SMB system.
In the process of sequence 1.2, carry out first displacement in forward position then.By making preceding two first displacement fields enter circulation, obtain this first displacement.First district of first displacement is the district that comprises post 3,4,5 and 6.Second district of first displacement is the district that comprises post 7,8,1 and 2.Uranium salt solution is injected post 3, and this causes first displacement in first district.Post 4 has the extracting solution that will purify then at the top.The content of post 6 reclaims in the bottom, and is the regenerative agent of dilution.Regenerative agent is injected post 7, and this causes first displacement in second district.Post 8 has regenerant solution at the top then.
In the process of sequence 1.3, carry out second displacement in forward position then.Enter circulation by two districts that make second displacement, obtain this second displacement.First district of second displacement is the district that comprises post 2,3,4 and 5.Second district of second displacement is the district that comprises post 6,7,8 and 1.Specifically water is injected post 2 and 6.Cause second displacement in forward position then.The composition at post 3 tops ends in post 4 tops; This is still the extracting solution that will purify.From this angle, in this second displacement process, the composition at post 4 tops is constant.Equally, the composition at post 8 acquisition posts 7 tops, i.e. regenerative agent.Still from this angle, the composition at post 8 tops is constant.What change in this second displacement process is composition in post 5 and 1, because obtain extract remainder in post 5 bottoms, obtains extract in post 1 bottom.In this second displacement process, between these two parts of production/regenerative process, form water " buffering " again to avoid the not pollution of jljl class.
In the 3rd embodiment, the displacement in forward position is asynchronous because the forward position that enters be not all with the same moved further in the forward position of leaving.In this example, make the forward position displacement that enters earlier, make the forward position displacement of leaving then, but also can be opposite.
In the 3rd embodiment, do not have subsequence that charging injects and be equivalent to subsequence 1.3 (or 2.3, depend on the sequence of being considered).
The post number in the corresponding zone needn't be constant in the displacement field or with regional (a) and (b), (c) with (d).Changing post number in each district has to benefit and makes full use of each post.For example, can have the constant first group of post (displacement post) that is in wash-out of number, production and renewing zone have variable-length simultaneously, for example are in post and post that is in regeneration of two productions, then post and two posts that are in regeneration that are in production.As another example,, can on M-1 or M-2 post or M-m post, have complete sequence (combination of all sequences (a) and (b), (c), (d) and displacement) if consider one group of M post.Can be then isolating one, two or m post on the resin bed or in the combination of series of valves that is connected with this post and conduit, for example to safeguard.
In fact, if necessary,, can be independent of the step that other post is selected on the post of selecting by the inventive method.The continuity method of prior art situation can not realize this point.For example, as previously mentioned, can isolate a post.Can in given sequence, change the supply of post thus.When post receives water, can use the water of recovery earlier, then fresh water is delivered on this post, thereby can be optimized water consumption.Also can supply variable charging or variable actified solution to post.With respect to method, can control rinsing better and produce stream according to the prior art situation.Especially, the method for prior art situation is by washings serial dilution aliment.This especially causes the speed (ion-exchange) of passing through in the adsorption zone to increase.Therefore, in the continuity method of prior art situation, there is not to observe the optimal hydraulic conditions of this each step of sequence.The present invention can utilize optimal hydraulic conditions better by moving each step in the best way, because the duration of step (a) and (b), (c) and (d) needn't be identical.Therefore optimized the stream in each post.
By making the fluid that leaves post be used further to follow-up post, can optimize this method to obtain best post supply flow.
Also can have the additional displacement post in other displacement post, particularly step (b), have the additional step of the water that is used to produce recovery thus.This embodiment is presented among Fig. 6, and it comprises 9 posts of use.Post 1 and 2 and 3 is equivalent to the post 1 and 2 and 3 among Fig. 3,4 and 5.Post 4 and 5 is equivalent to the post 4 among Fig. 3,4,5.Compare with 5 embodiment with Fig. 3,4, post 6 is new.Post 7 is equivalent to the post 5 and 6 among Fig. 3,4,5.Post 8 and 9 is equivalent to the post 7 and 8 among Fig. 3,4 and 5.Operational mode and Fig. 3,4 and 5 embodiment are identical.Enter circulation equally at this.Similarly, can followingly delimit two displacement fields according to second embodiment: first displacement field comprises post 2 to 7 and second displacement field comprises post 8,9 and 1.Therefore can delimit first and second displacement fields according to the 3rd embodiment.First and second districts of first displacement comprise post 3 and 7 on the one hand, comprise post 8 and 2 on the other hand.First and second districts of second displacement comprise post 2 to 7 on the one hand, comprise 8,9 and 1 on the other hand.In the embodiment of Fig. 6, leave the stream of post 3 and directly supply post 4.In the embodiment of Fig. 6 (the same) with other embodiment, the pH value that can regulate the different fractions of delivering on the post.For example, the pH value that can guarantee the fraction that contacted with the maximum post (is 3 at this) of load is being sent into before the post of back less than 2.By changing change pH values, also can change the type of the ionic metal derivative that preferentially is fixed on the resin.Also can on several posts, add extracting solution concurrently.
The present invention also is applicable to all types of products is carried out all types of chromatographic isolation.Especially, method of the present invention can be used 5 kinds of (or more) inlet flows:
-incoming flow (charging): this liquid contains charging and the pH buffer compositions thereof that will process, and by at this fluid of on-column injection, salinity can make desired molecule be adsorbed on and fixingly go up mutually.When the charging stage finished, this post contained the fixedly phase of having adsorbed the ionic metal derivative on it, and the liquid phase that is arranged in this post is made of dilution charging (FD).
-rinse streams has salinity identical with incoming flow and pH, but does not contain the charging that will process.This step is upgraded the liquid phase of this post, and can remove the feed compound that is not fixed and retains mutually.Under the situation that is uranium salt, use for example water or aqueous acid.
The wash-out of-required thing class: the fluid with the character that changes the interactional character between target molecule and the fixing phase can make target molecule go up desorb mutually from fixing, target molecule is collected in discharges in the liquid then.For the wash-out uranous sulfate, typical eluant, eluent is a sulfuric acid according to the present invention, and when this uranium is the uranium carbonate form, by sodium chloride or by ammonium carbonate or this complex compound of sodium carbonate liquor wash-out.
-regeneration: behind wash-out, impurity may still be adsorbed on securely to fix and go up mutually, and this may be harmful to its stability or spatter property.We understand, and under the situation of extraction uranium and copper, these pollutants can be silica or iron.Therefore can use the fluid that contains acid additive (for example sulfuric acid).Under the situation of described uranium salt, the elution step of required thing class and regeneration are carried out simultaneously before being, the site of regenerative agent (sulfuric acid) exchanger resin is to discharge uranium salt.
-with charging after the injection of the suitable solvent of used rinse streams can be from this post emptying regenerated solvent before carrying out next charging.Between charging and regeneration ending, keep buffering thus; This is a balance.
-optional the injection of polluting control stream can be removed the impurity of resin (particularly silica, it is attached to the uranium competition and limits charging and wash-out power on the resin thus) pollution.Usually, under situation of the present invention, can use alkali, preferred highly basic, for example NaOH or potassium hydroxide flow as depollution.
The invention provides the method that can implement 5 steps:
-step a: be known as balance, in this process, at least one post of this system, inject balance solution with from its contained regenerated solvent of this post emptying.In the downstream of this equilibrium area, the fluid of taking-up mainly is made of actified solution at first, mainly is made of balance solution then;
-step b: be known as charging, in this process, inject the feedstock solution that to process.Desired molecule is fixed on the chromosorb with other impurity then.The impurity of least retaining is contained in exit in this district that is positioned at the injection point downstream, the fluid of taking-up thereupon.
-step c: be known as washing, in this process, carry out the washing of this post, wherein contain the liquid phase of the impurity of not retaining especially with the cleaning solvent displacement.
-steps d: be known as wash-out, in this process, inject the interactional solution that changes between desired molecule and the chromosorb, wash-out desired molecule thus.In the exit of this elution zone, the fluid of taking-up contains rinsing solution at first, contains the solution that is rich in the ionic metal derivative then.
-step e: be known as regeneration, in this process, inject actified solution, thereby discharge the impurity that is adsorbed on very securely on the carrier.
In the present invention, can carry out the periodicity displacement of injection point from a post to a post ground; Therefore, can handle each post (or zone) independently.The present invention can operate each post (or zone) independently; Especially, can be synchronous or nonsynchronous as the displacement step in forward position, the displacement of injection/off-take point can be synchronous, nonsynchronous, and post (or zone) one by one carries out one by one.Also can operate a post (or zone) that is used for an operation, or operation is used for several posts (or zone) of other operation; Therefore can move the forward position of two or more posts of the forward position of a post of injection/off-take point and given area and another given area.
Fig. 7 has shown the method according to prior art, and it has synchronous a plurality of posts, periodically becomes sequence with non-, and comprises different fluid intakes.Between each these inlet, can the defined area: for example between charging (Feed) inlet and equilibrium liquid inlet, delimit feed zone.Between rinsing solution (Wash) and charging (Feed), delimit the rinsing district, or the like ... these zones corresponding to the first, second, third, fourth and the 5th district of the inventive method (under the situation of slaine and ion exchange resin, the the 4th and the 5th district can merge, and eluant, eluent and regenerative agent are same fluid).Also shown periodically displacement among Fig. 7.We see the principle shown in Fig. 1 (it is equivalent to the situation of four fluids) at this.
No. 9 posts endways are in the charging structure.After switching, it just is positioned at before the outlet of washing step.Therefore, just after pipeline switched, the effluent of this post still contained charging, therefore contained the ionic metal derivative that does not purify, and it in fact dilutes, and loss.
In the present invention, in fact feed pipe and each fluid intake pipe can move freely with respect to other pipe, and may have the consequence of forward position displacement.In fact, each of forward position time displacement can be pursued pipeline ground, synchronous or asynchronous ground (also by pipeline) carries out.All combinations are all feasible, and the displacement that it being understood that the forward position comprises the displacement in charging forward position at least, preferably also comprise the displacement in regenerative agent forward position.This displacement in forward position in this displacement at the post place that is in the charging stage, is impossible in the system of prior art situation at least.
Also can make the increment of a post of forward position displacement, but also can displacement less than or greater than the increment of a post.
Use asynchronous pattern, can reduce the sum of post by making several districts designated period of time that in same column, coexists.
Figure 11 is the example with the inventive method of several fluid lines (is 8 at this).In the situation shown in Figure 11, we have showed that aforesaid impurity separates.In this embodiment, to post 1 and 2 water of supplying as rinsing liquid, obtain the ionic metal derivative solution of dilution in the exit.To adsorption column 3 supply chargings, the effluent of pre-downstream simultaneously adsorption column supply post 3 (its can with the effluent of column scrubber 1---the feedstock solution of dilution merges), and obtain effluent (extract remainder) in the exit of pre-adsorption column.Post 5,6 and 7 is used for removing one or more impurity according to polluting control program (depending on the impurity of being considered).Under the situation that is silica, use NaOH to pollute control, use the regeneration of sulfuric acid resin then.After each procedure of processing, follow rinse step.Wash post 8 with water, effluent is mixed by sulfuric acid.This solution is eluent solution, is sent on post 9 and 10, and their effluent is an extract.This extract provides the ionic metal derivative, and the water that separates can recycle (being shown as the washing of returning post 1 and 2 at this) in the method.
Method described in Fig. 7 shows according to the periodicity method of sub-sequence not (wherein synchronously and not sub-sequence ground does not carry out the displacement of the injection pipeline of different solutions) implements these steps, and Figure 12 has shown the method for the asynchronous and sub-sequence of displacement.Therefore Figure 12 has shown the example of implementing process in accordance with the present invention (a) to (e) on 6 column systems, and the cycle of this system is divided into 5 subsequences, corresponding to the displacement of some injection pipeline in the various moment of this sequence.
When first sequence began, situation was as follows:
The injection pipeline of-balance solution is in post 1
The injection pipeline of-regeneration and elute soln is in post 2.As mentioned above, in the pipeline of stack,, be the elute soln injection pipeline in this case based on downstream line.
The injection pipeline of-column scrubber is in post 3
The injection pipeline of-the feedstock solution that process is in post 4.
This structure is equivalent to subsequence 1.1, and it continues to for example t=0.24* Δ t from t=0.
When subsequence 1.1 is finished, with the post displacement, wash-out pipeline for example.When subsequence 1.2 beginnings, be constructed as follows:
The injection pipeline of-balance solution is in post 1
The injection pipeline of-actified solution is in post 2
The injection pipeline of-elute soln is superimposed upon in the injection of cleaning solution in post 3.If based on downstream line, then in post 3, inject wash solution.
The injection pipeline of-the feedstock solution that process is in post 4.
Subsequence 1.2 continues to t=0.36* Δ t from for example t=0.24* Δ t.
When subsequence 1.2 is finished, for example make the sluicing pipe displacement of the lines.When subsequence 1.3 beginnings, be constructed as follows:
The injection pipeline of-balance solution is in post 1
The injection pipeline of-actified solution is in post 2
The injection pipeline of-elute soln is in post 3
The injection pipeline of-cleaning solution is superimposed upon on the injection pipeline of the feedstock solution that will process in post 4.If charging is positioned at the washing downstream, then based on feed injection.Therefore the feedstock solution that will process is injected post 4.
Subsequence 1.3 for example continues to t=0.60* Δ t from t=0.36* Δ t.
When subsequence 1.3 is finished, balance and the simultaneous displacement of regeneration pipeline.When subsequence 1.4 beginnings, be constructed as follows:
The injection pipeline of-balance solution is at post 2
The injection pipeline of-actified solution is superimposed upon on the injection pipeline of elute soln in post 3.Be that main downstream line is the injection of elute soln in this case.
The injection pipeline of-cleaning solution is superimposed upon on the injection pipeline of the feedstock solution that will process in post 4.If charging is positioned at the washing downstream, then based on feed injection.Therefore in post 4, inject the feedstock solution that to process.
Subsequence 1.4 for example continues to t=0.76* Δ t from t=0.60* Δ t.
When subsequence 1.4 is finished, carry out transition, ionic metal derivative contained in the liquid phase corresponding to post 4 is shifted to post 5.Therefore for this reason, stop to inject the feedstock solution that to process, exist from the transition of feed step (b), corresponding to the concentration forward position displacement of the liquid phase of impurity that makes not retention by step (c) and ionic metal derivative.Therefore this transition is to stop to inject the charging that will process, the displacement in the forward position that causes corresponding to step (c).
When subsequence 1.5 beginnings, be constructed as follows:
The injection pipeline of-balance solution is in post 2
The injection pipeline of-actified solution is superimposed upon on the injection pipeline of elute soln in post 3.Be that main downstream line is the injection of elute soln in this case.
The injection pipeline of-cleaning solution is at post 4.
Subsequence 1.5 for example continues to t=Δ t from t=0.76* Δ t.
When subsequence 1.5 was finished, finished first period, and the feedstock solution that will process is injected post 1.5.
Therefore the subsequence 2.1 of sequence 2 begins.Can notice that the subsequence 2.1 of sequence 2 is similar to the subsequence 1.1 of sequence 1, different is that pipeline moves 1 post.
Therefore as can be seen, by the asynchronous displacement of pipeline, can implement wash-out, regeneration and equilibrium step in sequence 1 on post 2, in fact, this compares with the method for using synchronous shift can reduce the post number.
Also can find out because the present invention, by with stop to inject the corresponding transitional sequence of feedstock solution (step (b)) that will process, can avoid when sequence 1.4 end, still being included in the loss of the ionic metal derivative in the post 4.
Also can use several eluant, eluent pipelines, contain the solution of several ionic metal derivatives of under different condition desorb or exchange with for example processing.By first eluant, eluent, can the selective recovery first ionic metal derivative, and by second eluant, eluent, can the selective recovery second ionic metal derivative.A kind of application examples comprises from Ruzhong recovery protein.
In description of the invention, term " post " it must be understood that to being meant the physics post, or when the physics post comprises injection and off-take point in several positions, refers to can be considered any other parts of the post of a unit.This can be divided into several fragments or unit the single physical major gene, and the present invention is applicable to this structure.
Therefore the present invention is fit to can be by any required product of chromatography separation.For example, the present invention can the isolating ions metal derivative, uranium salt for example, and wherein fixing is ion exchange resin mutually, and rinsing liquid is a water.
Embodiment
The non-limiting illustration the present invention of following embodiment.
Embodiment 1. ionic metal derivatives
Method of the present invention is applicable to all types of metal derivatives, uranium salt for example, and for example uranyl sulfate, nickel, cobalt or copper are by resin cation, with acid (for example sulfuric acid) wash-out.Therefore the present invention provides the method that the ionic metal derivative is separated with the extracting solution that contains this derivative and impurity, wherein make the ion exchange resin fixed bed at least four districts of described solution by comprising series connection, between the adjacent region and in the end between a district and first district liquid flow device is being set, described slaine is by contacting and optionally exchanged with described ion exchange resin, and at least a described impurity on this ion exchange resin than the less exchange of this slaine, make the exchange force regeneration of this ion exchange resin by the effect of regenerative agent, it is characterized in that it comprises several sequences, each sequence comprises the steps:
(a) introduce the water of certain volume and substantially side by side take out the diluted liquid of described slaine of equal volume at least in the position that is positioned at this downstream, zone in the porch in first district;
(b) introduce the described aqueous solution of certain volume in the porch in second district, with the liquid that is rich in the relative less impurity that is exchanged that substantially side by side takes out equal volume in the position that is positioned at downstream, described district;
(c) introduce the water of certain volume and substantially side by side take out the diluted liquid of eluant, eluent of equal volume in the porch in the 3rd district in the position that is positioned at downstream, described district;
(d) at the eluant, eluent of the porch in the 4th district introducing certain volume with substantially side by side at the liquid that is rich in described slaine that is positioned at described district location downstream taking-up equal volume;
Step (a) and (b), (c) and (d) can simultaneously or not carry out simultaneously;
Periodicity by introducing point and off-take point is the increment of the basic identical volume of displacement downstream, carries out the sequence of each back.
Also comprise step
(e) the forward position displacement in these zones before the periodicity displacement.
Under the situation that is uranyl sulfate, eluant, eluent is an acid solution.If the inventive method is compared with the continuation method of the known prior art situation that is used for uranyl salts production, this method has realized significant gain.For identical production, running stores greatly reduce, and water consumption reduces, and the waste liquid growing amount reduces, and the post number also reduces.
Embodiment 2. ionic metal derivatives, uranyl sulfate
In order to implement the separation of uranium, carry out following method.
Feed fluid (extracting solution that contains uranium and impurity thereof) contains the charging that will process.The composition of this fluid makes the ionic metal derivative to go up mutually attached to fixing.When feed step finished, this post contained fixedly phase, and uranyl sulfate is fixed thereon by ionic forces.
Rinse step is upgraded the liquid phase of this post thus, make impurity in the liquid phase be included in this post make impurity in the liquid phase that is included in this post in the process of elution step not with slaine wash-out simultaneously.
The eluent of uranyl sulfate is a 2M sulfuric acid.In fact, because the superregulated property of uranyl sulfate anion complex, it is verified to be the enough strong eluant, eluent of uranium I V.
Use 8 posts according to the test that the multicolumn partition method of the one-tenth sequence among this embodiment is carried out according to as shown in Figure 13 following sequence and subsequence.Each post of numbering for this sequence provides bed volume (BV) and duration.
Sequence 1
Subsequence 1.1: preceding 4 posts delimited feed zone.Post 5 is in the renewing zone.Post 1 and 4 and 5 and 7 series connection.Post 8 is in and pollutes control or standby.
Subsequence 1.2: in this subsequence, post 5 almost completely is reproduced, and no longer contains uranyl sulfate, and it enters the rinsing district then.
Subsequence 1.3: in this subsequence, the extracting solution that post 1 is almost contained the uranium that will extract is saturated, and it enters rinsing then.
Sequence 2
It is identical with sequence 1, but moves a post.
In described system, to test with 413 cubic metres/hour charging rate, this extracting solution contains the uranium of 0.35 grams per liter, and from the distinctive impurity of the charging of extraction.List the technological parameter that is used to separate this solution below.
Mean flow rate: 413 cubic metres/hour
1 time of subsequence: 3.43 hours
2 times of subsequence: 0.50 hour
3 times of subsequence: 0.21 hour
The step time: 4.14 hours
Resin capacity: 29.9 grams per liters.

Claims (15)

1. the multicolumn on resin is by the partition method of sequence, be used for by making the extracting solution that contains the ionic metal derivative described ionic metal derivative be separated with described extracting solution by the fixing resin bed that comprises at least three districts, between the adjacent district and in the end between a district and first district liquid flow device is being set, described method comprises several sequences, each sequence comprises the adsorption step that is selected from that at least one carries out simultaneously or do not carry out simultaneously, rinse step, the step of desorption procedure, the sequence of each back is following carries out: made the essentially identical increment of forward position downstream displacement in these districts before the periodicity displacement of introducing point and off-take point.
2. according to the method for claim 1, it is characterized in that it comprises several sequences, each sequence comprises at least one following step:
(a) introduce the rinsing solution of certain volume and substantially side by side take out the diluted liquid of described ionic metal derivative of equal volume in the porch in first district in the position that is positioned at downstream, described district;
(b) introduce the described charging extracting solution of certain volume in the porch in second district, with the liquid that is rich in the relative impurity of more not retaining that substantially side by side takes out equal volume in the position that is positioned at downstream, described district;
(c) introduce the rinsing solution of certain volume and substantially side by side take out the diluted liquid of regenerative agent of equal volume in the porch in the 3rd district in the position that is positioned at downstream, described district;
(d) randomly introduce the decontamination agent of certain volume and substantially side by side take out the dilution of equal volume in the position that is positioned at downstream, described district in the porch in the 4th district,
(e) introduce the eluant, eluent of certain volume and substantially side by side take out the liquid that is rich in described metal derivative of equal volume in the porch in the 5th district in the position that is positioned at downstream, described district;
Step (a) and (b), (c), (d) and (e) can carry out simultaneously or not carry out simultaneously;
The sequence of each back be by introduce point and off-take point periodically downstream the increment of mobile basic identical volume carry out;
Also comprise step:
(f) before the periodicity displacement, at least zone (b) and (e) in the displacement in forward position.
3. according to the method for one of claim 1 to 2, it is characterized in that step (d) and (e) carry out, these steps thereby be equivalent to the step of following formation with same fluid:
(d) introduce the regenerative agent of certain volume and substantially side by side take out the liquid that is rich in described ionic metal derivative of equal volume in the porch in the 4th district in the position that is positioned at downstream, described district;
The the described the 4th and the 5th district thereby be merged into the 4th single district.
4. according to the method for claim 1 to 3, it is characterized in that step (a) and (b), (c) and (d) carry out simultaneously to small part.
5. according to the method for one of claim 1 to 4, the described displacement that it is characterized in that the forward position makes the forward position synchronous shift in the same district not.
6. according to the method for claim 5, it is characterized in that the displacement in forward position comprises the steps:
(i) do not setting up the closed circuit district between the same district from five districts, first district to the; With
(ii) in described loop, circulate so that the forward position displacement.
7. according to the method for claim 5, it is characterized in that the displacement in forward position comprises the steps:
(i) be connected with the fluid of second district inlet by the outlet of first district and be connected by the fluid of second district outlet with the 3rd district inlet, set up first displacement field, and the displacement downstream of the inlet in first district with the outlet displacement upstream in inlet that first displacement field is provided and the 3rd district so that the outlet of first displacement field to be provided; With
Is connected with the fluid of the 4th district inlet and exports the fluid that enters the mouth with the 5th district by the 4th district and be connected and export the fluid that enters the mouth with first district with the 5th district and be connected by the 3rd district outlet, set up second displacement field, and the displacement downstream of the inlet in the 3rd district with the outlet displacement upstream in the inlet that second displacement field is provided and first district so that the outlet of second displacement field to be provided; With
(ii) introduce the rinsing solution of certain volume and substantially side by side take out the rinsing solution of the recovery of equal volume in the exit of first displacement field in the porch of first displacement field;
(iii) introduce the rinsing solution of certain volume and substantially side by side take out the rinsing solution of the recovery of equal volume in the exit of second displacement field in the porch of second displacement field.
8. according to the method for one of claim 1 to 4, the described displacement that it is characterized in that the forward position makes the asynchronous displacement in forward position in the same district not.
9. method according to Claim 8 is characterized in that the displacement in forward position comprises the steps:
(i) be connected with the fluid of second district inlet by the outlet of first district and be connected, set up first district of first displacement by the fluid of second district outlet with the 3rd district inlet; With
Is connected with the fluid of the 4th district inlet and exports the fluid that enters the mouth with the 5th district by the 4th district and be connected and export the fluid that enters the mouth with first district with the 5th district and be connected by the 3rd district outlet, set up second district of first displacement; With
(ii) introduce the described solution of certain volume and substantially side by side at the regenerative agent liquid of the dilution of the equal volume of the exit taking-up equal volume in first district of first displacement in the porch of first displacement field;
(iii) introduce the regenerative agent of certain volume and substantially side by side at the diluted liquid of described ionic metal derivative of the exit taking-up equal volume in second district of first displacement in the porch of second displacement field;
(iv) be connected with the fluid of second district inlet and be connected by the fluid of second district outlet with the 3rd district inlet by the outlet of first district, set up first district of second displacement, and the displacement downstream of the inlet in first district is with the outlet displacement upstream in the inlet in first district that second displacement is provided and the 3rd district outlet with first district that second displacement is provided; With
(v) be connected with the fluid of the 4th district inlet with being connected with the fluid of the 5th district outlet with the fluid of the 5th district inlet and be connected with first district inlet by the outlet of the 4th district by the outlet of the 3rd district, set up second district of second displacement, and the displacement downstream of the inlet in the 3rd district with the outlet displacement upstream in the inlet that second displacement field is provided and first district so that the outlet of second displacement field to be provided; With
(vi) introduce the rinsing solution of certain volume, with substantially side by side at the liquid that is rich in the relative impurity of more not retaining of the exit taking-up equal volume in first district of second displacement in the porch in first district of second displacement;
(vii) introduce the rinsing solution of certain volume and substantially side by side at the liquid that is rich in described ionic metal derivative of the exit taking-up equal volume in second district of second displacement in the porch in second district of second displacement.
10. according to the method for one of claim 1 to 9, it is characterized in that step (f) is included in moving of the forward position in all districts before the periodically displacement.
11., it is characterized in that the dilatation of described introducing point and described off-take point displacement is equivalent to the volume of the entire portion in absorbing material district substantially, preferably is equivalent to column volume substantially according to the method for one of claim 1 to 10.
12., it is characterized in that described liquid to the small part that described metal ion derivative is diluted is sent to step (b) according to the method for one of claim 1 to 11.
13. method according to one of claim 1 to 12, it is characterized in that existing additional zone, and be characterised in that it also comprises the rinsing solution that step (g) is introduced the diluted liquid of the described metal ion derivative of all or part acquisition in step (a) and reclaimed basic identical volume in the position that is positioned at downstream, described district in described additional zone.
14. method according to one of claim 1 to 13, it is characterized in that described chromatography is the ion-exchange type, and described ionic metal derivative is the salt that is selected from the complex compound of uranium, gold, copper, zinc, nickel, cobalt and PGM, preferably the salt of uranium, particularly uranous sulfate.
15., it is characterized in that described eluant, eluent is a sulfuric acid according to the method for one of claim 1 to 14.
CN2008801271499A 2007-12-20 2008-12-19 Multi-column sequenced separation process for separating an ionic metal derivative Active CN101945690B (en)

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FR0708966 2007-12-20
FR07/08966 2007-12-20
FR0708966A FR2925349A1 (en) 2007-12-20 2007-12-20 Separation on resin by multicolumn sequential selective retention to separate an ionic metal derivative e.g. uranium, gold, and zinc, from a leaching solution containing ionic metal derivative, by passing the solution on a fixed resin bed
PCT/FR2008/001797 WO2009106734A1 (en) 2007-12-20 2008-12-19 Multi-column sequenced separation process for separating an ionic metal derivative

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CA2709912C (en) 2016-09-06
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IL206422A0 (en) 2010-12-30
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AU2008351969A1 (en) 2009-09-03
FR2925349A1 (en) 2009-06-26

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